EP0564232B1 - Dérivés du N,N-bis(phosphonométhyl)-2-amino-1-propanol pour inhiber la formation de tartre à pH élevé - Google Patents

Dérivés du N,N-bis(phosphonométhyl)-2-amino-1-propanol pour inhiber la formation de tartre à pH élevé Download PDF

Info

Publication number
EP0564232B1
EP0564232B1 EP93302469A EP93302469A EP0564232B1 EP 0564232 B1 EP0564232 B1 EP 0564232B1 EP 93302469 A EP93302469 A EP 93302469A EP 93302469 A EP93302469 A EP 93302469A EP 0564232 B1 EP0564232 B1 EP 0564232B1
Authority
EP
European Patent Office
Prior art keywords
scale
acid
ampsa
phosphonomethyl
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93302469A
Other languages
German (de)
English (en)
Other versions
EP0564232A1 (fr
Inventor
Shih-Ruey Thomas Chen
Gary F. Matz
Raymond J. Schaper
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Calgon Corp
Original Assignee
Calgon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Calgon Corp filed Critical Calgon Corp
Publication of EP0564232A1 publication Critical patent/EP0564232A1/fr
Application granted granted Critical
Publication of EP0564232B1 publication Critical patent/EP0564232B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)

Definitions

  • the present invention relates to compositions and methods for inhibiting the formation, deposition and adherence of alkaline earth metal scale deposits, especially calcium carbonate (CaCO 3 ) scale deposits, on metallic surfaces of aqueous systems, especially under conditions of high pH and high calcite concentration, e.g., those found in cycled up cooling tower systems, where those compositions are N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers thereof.
  • alkaline earth metal scale deposits especially calcium carbonate (CaCO 3 ) scale deposits
  • calcium carbonate scale deposits are incrustation coatings which accumulate on the metallic surfaces of a water-carrying system through a number of different causes.
  • Calcium carbonate scale is of particular concern in heat exchange systems employing water, such as, for example, boiler systems, and once-through and open recirculating water cooling systems. Cooling towers are especially significant, particularly where severe conditions, including high pH and high calcite concentrations are encountered.
  • the water employed in these systems ordinarily will contain a number of dissolved salts, and the alkaline earth metal cation calcium is usually prevalent, as is the anion carbonate.
  • the combination product of calcium cation and carbonate anion will precipitate from the water in which they are carried to form scale deposits when the concentration of the anion and cation comprising the reaction product, i. e., calcium carbonate, exceeds the solubility of the reaction product itself.
  • concentrations of calcium ion and carbonate ion exceed the solubility of the calcium carbonate reaction product, a solid phase of calcium carbonate will form as a precipitate. Precipitation of the reaction product will continue until the solubility product concentrations of the constituent ions are no longer exceeded.
  • the mechanism of scale formation is apparently one of crystallization of scale-forming salts from a solution which is locally supersaturated in the region adjacent the heating surface of the system.
  • the thin viscous film of water in this region tends to become more concentrated than the remainder of the solution outside this region.
  • Precipitation is also favored on the heat transfer surface because of the inverse solubility relationship of calcium carbonate.
  • the solubility of the scale-forming calcium carbonate salt reaction product is first exceeded in this thin film, and crystallization of calcium carbonate scale results directly on the heating or heat exchange surface.
  • alkalinity of the makeup water results in an increasing alkalinity of the water in the overall system, often reaching pH's of 8.5 - 9.5 and even higher.
  • Conventional scale inhibiting compositions typically fail in systems having such severe conditions.
  • calcium carbonate scale deposits poses a serious problem in a number of regards.
  • the calcium carbonate scale which is formed possesses a low degree of heat conductivity.
  • a calcium carbonate scale deposit is essentially an insulating layer imposed across the path of heat travel from whatever source to the water of the system.
  • the retarded heat transfer causes a loss in cooling efficiency.
  • calcium carbonate scale formation facilitates underdeposit corrosive processes, and a substantial calcium carbonate scale deposit will interfere materially with fluid flow. Consequently, calcium carbonate scale is an expensive problem in many industrial water systems, causing delays and shutdowns for cleaning and removal.
  • the present invention is directed primarily to preventing or inhibiting the deposition of calcium carbonate scale, the most prevalent type of scale deposit, it is also applicable to inhibiting the deposition of other types of alkaline earth metal scales, especially where those are associated with calcium carbonate scale under the severe conditions described herein.
  • alkaline earth metal cations such as calcium and magnesium
  • anions such as bicarbonate, carbonate, and phosphate.
  • alkaline earth metal scales including but not limited to calcium carbonate, magnesium carbonate, and calcium phosphate. These scales form frequently in the tubes of heat exchangers and on other heat exchange surfaces, such as those in cooling towers. Particular systems or applications areas where severe conditions lead to exceptional buildup of calcium carbonate and related scales, in addition to cycled up cooling towers, include reverse osmosis systems, sugar refining evaporators, and certain types of gas scrubbers.
  • N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers of the present invention are used in the same range of amounts as threshold inhibitors in the scale inhibition method of the present invention, rather than as sequestering or chelating agents, although the compositions of the present invention have dispersant properties as well and significantly reduce the adherency of any scale deposit which is formed, facilitating its easy removal.
  • Scale-forming compounds can be prevented from precipitating by inactivating their cations with chelating or sequestering agents, so that the solubility of their reaction products is not exceeded. Generally, this requires many times as much chelating or sequestering agent as cation, since chelation is a stoichiometric reaction, and these amounts are not always desirable or economical. However, several decades ago, it was discovered that certain inorganic polyphosphates would prevent such precipitation when added in amounts far less than the concentrations needed for sequestering or chelating.
  • anionic and cationic polymers can be used as dispersants in accordance with methods known in the art, but the dosage levels necessary to achieve dispersion are in the range of 0.5 - 1.0% by weight of the system being treated, which is many orders of magnitude higher that the dosage levels used for the compositions of the present invention.
  • compositions of the present invention are especially useful under severe conditions characterized by a calcite saturation level of 150 X and above, especially 250X and above, and more especially 300X and above, as defined in the paragraph immediately below.
  • Another characteristic feature of the severe conditions under which the scale controlling compositions of the present invention are especially useful is high pH, i.e. a pH of 8.5 and higher, particularly a pH of 9 or 10 or even higher.
  • a related feature of such severe conditions is high alkalinity.
  • Calcium tolerance is a measure of a chemical compound's ability to remain soluble in the presence of calcium ions (Ca 2+ ).
  • Ca 2+ calcium ions
  • One of the parameters of scale control under severe conditions is pH.
  • CaCO 3 threshold inhibitors e.g., 1-hydroxy ethylidene 1,1-diphosphonic acid (HEDP) and amino tri(methylene phosphonic acid) (AMP). These inhibitors precipitate with calcium at alkaline pH's, rendering them useless as threshold scale inhibitors.
  • An advantage of the scale inhibiting compositions of the present invention is their ability to maintain a level of resistance to degradation by oxidizing biocides which is sufficient to ensure adequate scale inhibition at dosing levels within the ranges herein described. This is of particular importance in cooling systems such as those using cycled up cooling towers. Such systems maintain a large body of water for a considerable length of time exposed to the atmosphere under conditions which do not include sufficient aeration and exposure to sunlight to provide control of microbial, especially bacterial and fungal, growth. Unchecked, such microorganisms flourish and produce colonies extensive enough to give rise to problems of biofilm blockage of heat exchange surfaces, and clogging of the components of the water transporting apparatus used in operating the cooling system.
  • threshold active inhibitor Another type of agent which has been actively explored heretofore as a calcium carbonate scale inhibiting material is the threshold active inhibitor.
  • Such materials are effective as scale inhibitors in amounts considerably less than that stoichiometrically required, and this amount, as already mentioned, is termed the threshold amount.
  • Inorganic polyphosphates have long been used as such threshold active inhibitors. For examples of such materials, see Fink - US 2,358,222; Hatch - US 2,539,305; and Ralston US 3,434,969.
  • Certain water soluble polymers including groups derived from acrylamide and acrylic acid have been used to condition water containing scale-forming calcium carbonate.
  • anionic polyelectrolytes such as polyacrylates, polymaleic anhydrides, copolymers of acrylates and sulfonates, and polymers of sulfonated styrenes. See, for example, US 4,640,793; 4,650,591; 4,457,847 ; and 4,671,888.
  • large dosages of these polymers are required, which in turn increases operating costs.
  • N,N-bis(phosphonomethyl)-2-amino-1-propanol and corresponding lower alkyl ethers of the type which comprise the active ingredient of the compositions of the present invention are known, nor is their use for the control of alkaline earth metal scale, particularly calcium carbonate scale, under severe conditions which include elevated pH and high calcium carbonate saturation levels, with enhanced resistance to degradation by oxidizing biocides. Nevertheless, other phosphonates of related structure are known in the art for scale inhibition use.
  • US 4,080,375 discloses methylene phosphonates of amino-terminated oxyalkylates for use as scale inhibitors, but these compositions are not the same as those of the present invention, nor is there any suggestion that such compositions would be useful under severe conditions as defined herein, where phosphonates such as HEDP and AMP give poor results.
  • US 4,931,189 discloses aminomethylene phosphonates for inhibiting oil field scale formation involving a high brine environment susceptible to gypsum or barite scale formation. Such use in no way suggests the control of scale under the severe conditions described herein under which the compositions and methods of the present invention operate with surprising success.
  • the present invention relates to a compound of the formula: where n is an integer of from 1 to 3, inclusive; M is hydrogen or a suitable cation; and R is independently selected from hydrogen and C 1-4 alkyl;
  • the present invention particularly relates to compounds of the above formulas wherein R is hydrogen, M is hydrogen, and n is 1, giving the compound N,N-bis(phosphonomethyl)-2-amino-1-propanol; and wherein R is methyl, M is hydrogen, and n is 1, giving the compound N,N-bis(phosphonomethyl)-1-methoxy-2-propanamine.
  • the present invention further relates to a composition useful as a deposit control agent to control the formation, deposition and adherency of scale imparting compounds in an aqueous system, comprising N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers therof, of the following formula: where n is an integer of from 1 to 3, inclusive; M is hydrogen or a suitable cation; and R is independently selected from hydrogen and C 1-4 alkyl.
  • the present invention also relates to a composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds in an aqueous system
  • a composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds in an aqueous system
  • the present invention further relates to a method of inhibiting the formation, deposition and adherence of scale-forming salts in an aqueous system, comprising the step of adding to said system an amount sufficient to establish a concentration of from 1 to 100 mg/L of N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers.
  • the present invention relates to such a method in which calcium carbonate is the scale-forming salt, the aqueous system comprises a cooling tower, and said compound is added to the aqueous system being treated in an amount sufficient to establish a concentration of from 10 to 50 mg/L.
  • the present invention further relates to a method of inhibiting the formation, deposition and adherence of scale-forming salts in an aqueous system, comprising the step of adding to said system an amount sufficient to establish a concentration of from 1 to 100 mg/L of a composition comprising N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers and N-oxides of the formula above, together with one or more members selected from the group consisting of: homo- and copolymers including terpolymers comprising one or more of acrylamide (AM), acrylic acid (AA), 2-acrylamide--methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid (IA), polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic
  • the present invention relates to such a method in which calcium carbonate is the scale-forming salt, the aqueous system comprises a cooling tower, said composition is added to the aqueous system being treated in an amount sufficient to establish a concentration of from 10 to 50 mg/L, and said polymer additive is a member selected from the group consisting essentially of 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA, 100 AA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively), and AA/AMPSA/TBAM.
  • the group consisting essentially of 90/10 to 10/90 AA/AMPSA preferably 75/25 and 60/40 AA/AMPSA, 100 AA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70
  • composition of the present invention useful as a deposit control agent to control the formation, deposition and adherency of scale imparting compounds in an aqueous system comprises N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers and N-oxides of the formula: where n is an integer of from 1 to 3, inclusive; M is hydrogen or a suitable cation; and R is independently selected from hydrogen and C 1-4 alkyl.
  • This key feature of the compounds of the present invention confers significant resistance to degradation by oxidizing biocides, presumably by preventing oxidative attack on the nitrogen atom of the group.
  • compositions of the above formula is that wherein M is hydrogen, n is from 1 to 3, more preferably 1, and R is hydrogen, methyl or ethyl, most preferably hydrogen or methyl.
  • M is hydrogen
  • n is from 1 to 3, more preferably 1
  • R is hydrogen, methyl or ethyl, most preferably hydrogen or methyl.
  • this group is present initially in the phosphonic acid form or as an alkali metal or other salt of the acid, has no critical bearing on the performance of the overall molecule.
  • the compositions of the present invention At the pH's under which the compositions of the present invention function, they are, and must be, in their ionized form.
  • M is hydrogen or a suitable cation, and the selection of an appropriate salt form is well within the skill of the art. Alkali metal salts are the most simple, and are preferred for that reason. Overall, however, it is preferred that M is hydrogen.
  • the most essential structural feature of the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers useful in the compositions and methods of the present invention is the isopropyloxy group, or series of repeating isopropyloxy groups, up to 3 in number, which bridge the diphosphonomethylamino group and the terminal hydrogen (hydroxyl) or lower alkyl ether (lower alkoxyl) group:
  • the isopropyloxy group has been found to be unique in providing enhanced scale inhibition activity under the severe conditions defined herein.
  • n 1
  • the isopropyloxy groups increase in number, there is a gradual decrease in the scale inhibiting efficiency of the overall compound.
  • all of these compounds continue to reflect the surprising improvement in performance attributable to the presence of the isopropyloxy group, whether one or more of such groups is present.
  • R is preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl, and most preferably methyl.
  • the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers of the compositions and methods of the present invention are prepared by phosphonomethylation of the appropriate primary amine which already contains the isopropyloxy moiety or moieties.
  • Such primary amine starting materials and their method of preparation are well known.
  • the phosphonomethylation of the primary amine is then carried out by a Mannich reaction such as that described in K. Moedritzer and R. Irani, J. Organic Chem. 31(5) 1603-7, "The Direct Synthesis of alpha-Aminomethyl Phosphonic Acids; Mannich-Type Reactions with Orthophosphorous Acid", May 1966.
  • the primary amine is added to a mixture of phosphorous acid and water, and concentrated hydrochloric acid is then added slowly, after which the reaction mixture is heated to reflux with addition of aqueous formaldehyde.
  • any of the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ether compositions of the present invention are used to inhibit the precipitation, deposition, and adherence of scale-forming salts in an aqueous system, they can be effectively employed for that purpose when added in amounts sufficient to establish a concentration in said aqueous system of from 1 to 100 mg/L.
  • the amount added will be sufficient to establish a concentration of from 5 to 75 mg/L, and most preferably, the amount added will be sufficient to establish a concentration of from 10 to 50 mg/L of the composition.
  • the amounts of that combination which must be added in order to inhibit the formation, deposition and adherence of scale-forming salts in an aqueous system will as a general matter be within the ranges of amounts sufficient to establish the ranges of concentrations of the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers used alone, as recited in detail above. Again, however, calculation of the actual amount is well within the skill of the art.
  • inhibitors the precipitation and “inhibiting the formation and deposition” are meant to include threshold inhibition, dispersion, solubilization, or particle size reduction.
  • inhibitors the adherence and “increasing the non-adherence”, are meant to define the formation of a scale deposit which is easily removed, e.g., by simple rinsing, i.e., a scale deposit which is not so firmly bonded to the surface to which it is attached that it cannot be removed by simple physical means as opposed to harsh mechanical or chemical treatment.
  • scale-forming salts is meant to include any of the scale-forming salts selected from the group consisting essentially of calcium carbonate, calcium phosphate, calcium phosphonate (including calcium hydroxyethylidene diphosphonic acid), and the corresponding magnesium salts.
  • aqueous system means commercial or industrial systems utilizing water and involving heat exchange surfaces, usually of metal, including cooling water systems including cooling towers, boiler water systems, desalination systems, gas scrubbers, and thermal conditioning equipment. Of particular importance are those systems which operate under severe conditions as detailed herein, including at least high pH and high calcite concentrations. Typical of such systems are cycled up cooling towers, reverse osmosis systems, sugar refining evaporators, and certain types of gas scrubbers.
  • N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivative, or corresponding lower alkyl ether composition of the present invention to an aqueous system will also be straightforward to a person of ordinary skill in this art. It may be added in liquid form by mechanical dispensers of known design. It may also be added in diluted liquid form. The N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivative, or corresponding lower alkyl ether composition may also be combined with other chemical treatment agents for dispensing to the aqueous system; and these in combination may be dispensed in liquid form.
  • acrylamide acrylamide
  • AA acrylic acid
  • AMPSA 2-acrylamide--methyl propane sulfonic acid
  • MAA methacrylic acid
  • IA itaconic acid
  • PGM polyethylene glycol monomethacrylate
  • MA maleic anhydride
  • MA maleic acid
  • TBAM t-butyl acrylamide
  • SSS sodium styrene sulfonate
  • AHPS 3-allyloxy-2-hydroxy propane sulfonic acid
  • vinyl phosphonic acid weight average molecular weight
  • compositions include copolymers of 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA.
  • Other preferred polymer additives for use with the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers and N-oxides of the present invention include 100 AA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively), (having 5 repeating oxyethylene units), and AA/AMPSA/TBAM.
  • Combinations using these polymers together with the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivative, or corresponding lower alkyl ether compositions of the present invention can increase the amount of scale control and deposit control which is achieved under the severe conditions described herein.
  • PROCEDURE Scaling water containing 250 mg/L of CO -2 / 3 and 600 mg/L of alkalinity at a pH of 9.0 and 55°C was used to evaluate scale inhibition performance of test solutions over a 24 hr period. Test solutions were analyzed by withdrawing 10 g of test solution and adding it to the appropriate container through a 0.2 ⁇ filter, titrating for calcium, and calculating % inhibition by the Schwarzenbach method.
  • the primary amine 1-methoxy-2-propanamine having the structural formula: CH 3 OCH 2 CH(CH 3 )NH 2 (22.28g, 0.25 mole) was added to a mixture of 70% phosphorous acid (58.57g, 0.50 mole), 50 mL of concentrated hydrochloric acid, and deionized water (32.43g) in a 250 mL 3-neck flask fitted with a condenser, a magnetic stirrer, a thermometer and an addition funnel. The reaction mixture was then heated to reflux, and there was then added 81.16g (1.00 mole) of 37% aqueous formaldehyde (HCHO) over a period of about 25 min. The reaction mixture was then refluxed for an additional period of 3 hrs. to complete the reaction. The reaction mixture was then reduced by 20% to yield an aqueous solution of 46.4%. Analysis of the 31 P NMR spectra of this solution indicated the desired product.
  • HCHO 37% aqueous formaldehyde

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (12)

  1. Composés de formule :
    Figure 00390001
    dans laquelle n est un nombre entier de 1 à 3, bornes comprises, M est l'hydrogène ou un cation approprié, et R est choisi indépendamment parmi l'hydrogène et un radical alkyle en C1 à C4.
  2. Un composé selon la revendication 1, dans lequel R est l'hydrogène, M est l'hydrogène et n est 1, ce qui donne le composé N,N-bis(phosphonométhyl)-2-amino-1-propanol.
  3. Un composé selon la revendication 1, dans lequel R est un radical méthyle, M est l'hydrogène et n est 1, ce qui donne le composé N,N-bis(phosphonométhyl)-1-méthoxy-2-propanamine.
  4. Une composition utile comme agent de régulation de dépôt pour réguler la formation, le dépôt et l'adhésion de composés produisant du tartre dans un système aqueux, comprenant un composé selon l'une quelconque des revendications 1 à 3.
  5. Un procédé pour inhiber la formation, le dépôt et l'adhésion de sels formant du tartre dans un système aqueux, comprenant l'étape consistant à ajouter audit système une quantité suffisante pour établir une concentration de 1 à 100 mg/l d'une composition selon la revendication 4.
  6. Un procédé selon la revendication 5, dans lequel le carbonate de calcium est le sel formant du tartre et ladite composition est ajoutée au système aqueux qui est traité selon une quantité suffisante pour établir une concentration de 10 à 50 mg/l.
  7. Un procédé pour inhiber la formation, le dépôt et l'adhésion de sels formant du tartre dans un système aqueux, comprenant l'étape consistant à ajouter audit système une quantité suffisante pour établir une concentration de 1 à 100 mg/l d'une composition comprenant un composé selon l'une quelconque des revendications 1 à 3, conjointement avec un ou plusieurs éléments choisis parmi le groupe comprenant :
    les homopolymères, les copolymères et les terpolymères comprenant un ou plusieurs monomères d'acrylamide (AM), d'acide acrylique (AA), d'acide 2-acrylamide-méthyl-propane sulfonique (AMPSA), d'acide méthacrylique (MAA), de méthacrylate éthoxylé, d'acide itaconique (IA), de polyéther-esters d'acide acrylique et d'acide méthacrylique et de polyéthers à base d'oxyde de polyéthylène et d'oxyde de polypropylène et de leurs mélanges, comprenant le monométhacrylate de polyéthylèneglycol (PGM), l'anhydride maléique (MA), l'acide maléique (MA), le t-butyl-acrylamide (TBAM), le styrène-sulfonate de sodium (SSS), le vinyl-sulfonate de sodium, l'acrylate d' hydroxy-propyle, le méthacrylate d' hydroxy-propyle, l'acide 3-allyloxy-2-hydroxy-propane sulfonique (AHPS), et l'acide vinyl-phosphonique, où le poids moléculaire moyen en poids pour de tels additifs polymères se situe dans la gamme d'environ 500 à 250 000.
  8. Un procédé selon la revendication 7, dans lequel l'additif polymère est choisi parmi le groupe comprenant l'acide polyacrylique et les copolymères 75/25 et 60/40 AA/AMPSA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/PGM-5 (ayant 5 motifs oxyéthylène se répétant), et AA/AMPSA/TBAM.
  9. Un procédé selon la revendication 8, dans lequel le carbonate de calcium est le sel formant du tartre et ledit propanol et ledit additif polymère sont ajoutés conjointement au système aqueux qui est traité selon une quantité suffisante pour établir une concentration de 10 à 50 mg/l.
  10. Un procédé selon la revendication 9, dans lequel le système aqueux qui est traité est un système de refroidissement.
  11. Une composition utile comme un agent de régulation de dépôt pour réguler la formation, le dépôt et l'adhésion de composés produisant du tartre dans un système aqueux comprenant, en combinaison, un composé selon l'une quelconque des revendications 1 à 3, conjointement avec un ou plusieurs éléments choisis parmi le groupe comprenant :
    les homopolymères, les copolymères incluant les terpolymères comprenant un ou plusieurs monomères d'acrylamide (AM), d'acide acrylique (AA), d'acide 2-acrylamide-méthyl-propane-sulfonique (AMPSA), d'acide méthacrylique (MAA), de méthacrylate éthoxylé, d'acide itaconique (IA), de polyéther-esters d'acide acrylique et d'acide méthacrylique et de polyéthers à base d'oxyde de polyéthylène et d'oxyde de polypropylène et leurs mélanges, comprenant le monométhacrylate de polyéthylène-glycol (PGM), l'anhydride maléique (MA), l'acide maléique (MA), le t-butyl-acrylamide (TBAM), le styrène-sulfonate de sodium (SSS), le vinyl-sulfonate de sodium, l'acrylate d'hydroxypropyle, le méthacrylate d'hydroxy-propyle, l'acide 3-allyloxy-2-hydroxy-propane-sulfonique (AHPS), et l'acide vinyl-phosphonique, dans lequel le poids moléculaire moyen en poids pour ces additifs polymères se situe dans la gamme d'environ 500 à 250 000.
  12. Une composition selon la revendication 11, dans laquelle l'additif polymère est choisi parmi le groupe comprenant l'acide polyacrylique et les copolymères 75/25 et 60/40 AA/AMPSA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/PGM-5 (ayant 5 motifs oxyéthylène se répétant), et AA/AMPSA/TBAM.
EP93302469A 1992-03-30 1993-03-30 Dérivés du N,N-bis(phosphonométhyl)-2-amino-1-propanol pour inhiber la formation de tartre à pH élevé Expired - Lifetime EP0564232B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US860373 1992-03-30
US07/860,373 US5259974A (en) 1992-03-30 1992-03-30 N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers and N-oxides thereof for high PH scale control

Publications (2)

Publication Number Publication Date
EP0564232A1 EP0564232A1 (fr) 1993-10-06
EP0564232B1 true EP0564232B1 (fr) 2000-06-07

Family

ID=25333078

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93302469A Expired - Lifetime EP0564232B1 (fr) 1992-03-30 1993-03-30 Dérivés du N,N-bis(phosphonométhyl)-2-amino-1-propanol pour inhiber la formation de tartre à pH élevé

Country Status (7)

Country Link
US (1) US5259974A (fr)
EP (1) EP0564232B1 (fr)
JP (1) JPH0649081A (fr)
AU (1) AU662212B2 (fr)
CA (1) CA2092493C (fr)
DE (1) DE69328801T2 (fr)
MX (1) MX9301755A (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322636A (en) * 1992-03-30 1994-06-21 Calgon Corporation Polyether polyamino methylene phosphonate n-oxides for high pH scale control
US5772893A (en) * 1996-08-13 1998-06-30 Nalco Chemical Company Ether diphosphonate scale inhibitors
US5788857A (en) * 1996-10-23 1998-08-04 Nalco Chemical Company Hydroxyimino alkylene phosphonic acids for corrosion and scale inhibition in aqueous systems
US6083403A (en) * 1998-11-05 2000-07-04 Nalco Chemical Company Stabilized substituted aminomethane-1, 1-diphosphonic acid n-oxides and use thereof in preventing scale and corrosion
US6333005B1 (en) 1999-06-16 2001-12-25 Hercules Incorporated Methods of preventing scaling involving inorganic compositions in combination with copolymers of maleic anhydride and isobutylene, and compositions therefor
US6355214B1 (en) * 1999-06-16 2002-03-12 Hercules Incorporated Methods of preventing scaling involving inorganic compositions, and inorganic compositions therefor
US6932909B2 (en) * 2002-01-15 2005-08-23 Kroff Chemical Company, Inc. Method of treating mine drainage
US6797197B2 (en) * 2002-08-30 2004-09-28 Johnsondiversey, Inc. Modified amine for boiler water treatment
EP1979366A4 (fr) * 2006-01-10 2011-05-25 Ruey J Yu Acides n-(phosphonoalkyl)-amines, derives, compositions et procedes d'utilisation associes
US7807021B2 (en) * 2006-06-21 2010-10-05 Blackstone Michael M Compositions and processes to increase pulp yield, reduce extractives, and reduce scaling in a chemical pulping process
WO2015088561A1 (fr) * 2013-12-13 2015-06-18 Halliburton Energy Services, Inc. Procédés et systèmes pour l'acidification de formations souterraines
US9765286B2 (en) * 2014-12-22 2017-09-19 Ecolab Usa Inc. Warewashing composition containing alkanol amine phosphonate and methods of use
CA3228118A1 (fr) * 2021-08-14 2023-02-23 Dorf Ketal Brasil Ltda, Brazil Phosphonates fonctionnalises, et sels solubles dans l'eau et leurs derives n-oxyde, et leur procede d'utilisation comme inhibiteur de tartre

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2358222A (en) * 1940-05-11 1944-09-12 Nat Aluminate Corp Art of treating water for industrial consumption
US2539305A (en) * 1943-10-09 1951-01-23 Hall Lab Inc Threshold treatment of water
US2783200A (en) * 1951-11-03 1957-02-26 Dearborn Chemicals Co Sludge conditioning and dispersing agents for boiler water treatment
US2980610A (en) * 1956-07-13 1961-04-18 Monsanto Chemicals Process for treating water
US3285886A (en) * 1961-07-17 1966-11-15 Grace W R & Co Threshold treatment of water with water dispersible complexing polymers
US3463730A (en) * 1965-08-05 1969-08-26 American Cyanamid Co Prevention of and removal of scale formation in water systems
US3514476A (en) * 1966-09-28 1970-05-26 Monsanto Co Making basic zinc double salts of o,o-dialkyl phosphorodithioic acids
US3434969A (en) * 1967-08-11 1969-03-25 Calgon Corp Scale inhibiting
US3518204A (en) * 1967-11-01 1970-06-30 Betz Laboratories Control of the rate of precipitate growth and of precipitation in aqueous systems
US4080375A (en) * 1971-02-05 1978-03-21 Petrolite Corporation Methylene phosphonates of amino-terminated oxyalkylates and uses therefor
US3928196A (en) * 1973-12-05 1975-12-23 Calgon Corp Inhibition of scale deposition
US3965027A (en) * 1974-03-11 1976-06-22 Calgon Corporation Scale inhibition and corrosion inhibition
US4088574A (en) * 1974-03-27 1978-05-09 Petrolite Corporation Employing methylene phosphonates of oxyalkylated polyalkylene polyamines in chelation and/or scale inhibition
US4457847B2 (en) * 1981-11-05 1996-12-31 Nalco Chemical Co Carboxylate polymers for internal scale control agents in boiler systems
US4936987A (en) * 1983-03-07 1990-06-26 Calgon Corporation Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers
US4640793A (en) * 1984-02-14 1987-02-03 Calgon Corporation Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers
US4671888A (en) * 1984-12-03 1987-06-09 Calgon Corporation Polyelectrolyte and surfactant compositions for controlling alkaline earth metal scales
US4650591A (en) * 1985-08-29 1987-03-17 Calgon Corporation Acrylic acid/2-acrylamido-2-methylpropylsulfonic acid/2-acrylamido-2-methylpropyl phosphonic acid polymers as scale and corrosion inhibitors
US4950474A (en) * 1988-08-01 1990-08-21 Texaco Inc. Combination corrosion and scale inhibiting system containing phosphonate/amine reaction product
US4931189A (en) * 1988-11-02 1990-06-05 Petrolite Corporation Methods for inhibition of scale in high brine environments
US5069798A (en) * 1989-12-15 1991-12-03 W. R. Grace & Co.-Conn. Control of scale in aqueous systems using certain phosphonomethyl amines
US4973744A (en) * 1989-12-15 1990-11-27 W. R. Grace & Co.-Conn. Ethoxylated N,N-bis-phosphonomethyl 2-(hydroxy)ethylamine N-oxides and water-soluble salts thereof
DE69217580T2 (de) * 1991-05-31 1997-06-26 Calgon Corp Polyether-Polyamino-Methylenphosphonaten zur Kontrolle von Ablagerungen bei hohem pH-Wert
US5322636A (en) * 1992-03-30 1994-06-21 Calgon Corporation Polyether polyamino methylene phosphonate n-oxides for high pH scale control
CA2092492A1 (fr) * 1992-03-30 1993-10-01 Ecc Specialty Chemicals Inc. N-(2-hydroxyethyl)-n-bis (acide methylenephosphonique) et son n-oxyde correspondant utilise pour reduire l'entartrage a ph eleve

Also Published As

Publication number Publication date
JPH0649081A (ja) 1994-02-22
AU3558393A (en) 1993-10-07
CA2092493A1 (fr) 1993-10-01
MX9301755A (es) 1994-08-31
DE69328801D1 (de) 2000-07-13
AU662212B2 (en) 1995-08-24
DE69328801T2 (de) 2001-02-22
US5259974A (en) 1993-11-09
CA2092493C (fr) 2006-12-19
EP0564232A1 (fr) 1993-10-06

Similar Documents

Publication Publication Date Title
US5358642A (en) Polyether polyamino methylene using phosphonates method for high pH scale control
US5338477A (en) Polyether polyamino methylene phosphonates for high pH scale control
US5565106A (en) Stabilization of polyether polyamino methylene phosphonate scale inhibitors against degradation by bromine and chlorine biocides
US5534157A (en) Polyether polyamino methylene phosphonates for high pH scale control
EP0564232B1 (fr) Dérivés du N,N-bis(phosphonométhyl)-2-amino-1-propanol pour inhiber la formation de tartre à pH élevé
AU664426B2 (en) N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide thereof for high pH scale control
US5322636A (en) Polyether polyamino methylene phosphonate n-oxides for high pH scale control
US5707529A (en) Method for controlling scale in an aqueous system using a synergistic combination
US5580462A (en) Controlling calcium carbonate and calcium phosphate scale in an aqueous system using a synergistic combination
US5772913A (en) Aqueous system containing a synergistic combination for scale control
AU719896B2 (en) A method for controlling scale in an aqueous system using a synergistic combination
US5593595A (en) Method for controlling scale using a synergistic phosphonate combination
US5709814A (en) Aqueous system containing a synergistic phosphonate scale control combination
US5702634A (en) Aqueous system containing a synergistic combination including polyether polyamino methylene phosphates for controlling calcium carbonate and calcium phosphate scale
EP0767145B1 (fr) Utilisation d'une composition synergique pour contrôler l'incrustation
CA2187121A1 (fr) Systeme aqueux contenant un complexe de phosphonate, servant a limiter le tartre
CA2187145A1 (fr) Systeme aqueux contenant un complexe synergique et servant a eliminer le tartre de carbonate de calcium et de phosphate de calcium
MXPA96004569A (en) An aqueous system containing a synergistic combination for controlling calcium and phosphate calculation incrustations
MXPA96004570A (en) An aqueous system that contains a synergistic combination for the control of defrosf incrustations

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB

17P Request for examination filed

Effective date: 19940308

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CALGON CORPORATION

17Q First examination report despatched

Effective date: 19990301

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB

REF Corresponds to:

Ref document number: 69328801

Country of ref document: DE

Date of ref document: 20000713

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20090327

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20090430

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20090317

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20090403

Year of fee payment: 17

BERE Be: lapsed

Owner name: *CALGON CORP.

Effective date: 20100331

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100330

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20101130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101001

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100330